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Annulation and cycloaromatization reactions of 3-aryl (alkyl) thio-1-trimethylsiloxy-1-methoxy-1,3-butadienes

The title compounds were synthesized from methyl 3-aryl(alkyl)thio crotonic acids by deprotonation followed by silylation. The reactions of dienes with a number of carbonyl electrophiles under Lewis-acid catalysed conditions were investigated. The dienes exclusively give $ gamma$-alkylated products. The thio substituent enhances the $ gamma$-selectivity. / The reactions of dienes with a number of 1,3-dicarbonyl equivalents have been studied and a cycloaromatization reaction has been developed for the regiocontrolled synthesis of aryl sulfides in a 3C + 3C combination. The role of dienes in Diels-Alder reactions has also been investigated. / A new 4C + 2C annulation reaction has been developed based on the propensity of dienes to undergo Michael reaction with $ alpha$,$ beta$-unsaturated ketones under Lewis-acid catalysed conditions. These Michael adducts in turn were cyclized either with potassium tert-butoxide or with lithium thiophenoxide. Further, the tandem Michael-Claisen annulation reaction can be controlled to give either cis- or trans-fused 9-methyldecalin system with three carbonyl groups which are differently masked. The chemoselective transformations of the carbonyl groups were also described.

Identiferoai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.75442
Date January 1986
CreatorsPrasad, Chaturvedula V.
PublisherMcGill University
Source SetsLibrary and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada
LanguageEnglish
Detected LanguageEnglish
TypeElectronic Thesis or Dissertation
Formatapplication/pdf
CoverageDoctor of Philosophy (Department of Chemistry.)
RightsAll items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated.
Relationalephsysno: 000554103, proquestno: AAINL44366, Theses scanned by UMI/ProQuest.

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